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EP0094142B1 - Druckplatte und Verfahren zu ihrer Herstellung - Google Patents

Druckplatte und Verfahren zu ihrer Herstellung Download PDF

Info

Publication number
EP0094142B1
EP0094142B1 EP83301216A EP83301216A EP0094142B1 EP 0094142 B1 EP0094142 B1 EP 0094142B1 EP 83301216 A EP83301216 A EP 83301216A EP 83301216 A EP83301216 A EP 83301216A EP 0094142 B1 EP0094142 B1 EP 0094142B1
Authority
EP
European Patent Office
Prior art keywords
epoxy
resin
novolac
composition
epoxy resin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP83301216A
Other languages
English (en)
French (fr)
Other versions
EP0094142A1 (de
Inventor
Anthony William Rigg
Phillip Rodney Kellner
Mohammed Aslam Sahi
Alan Raymond Gamson
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Crosfield Electronics Ltd
Original Assignee
Crosfield Electronics Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Crosfield Electronics Ltd filed Critical Crosfield Electronics Ltd
Publication of EP0094142A1 publication Critical patent/EP0094142A1/de
Application granted granted Critical
Publication of EP0094142B1 publication Critical patent/EP0094142B1/de
Expired legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
    • B41N1/00—Printing plates or foils; Materials therefor
    • B41N1/12—Printing plates or foils; Materials therefor non-metallic other than stone, e.g. printing plates or foils comprising inorganic materials in an organic matrix
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C1/00—Forme preparation
    • B41C1/02—Engraving; Heads therefor
    • B41C1/04—Engraving; Heads therefor using heads controlled by an electric information signal
    • B41C1/05—Heat-generating engraving heads, e.g. laser beam, electron beam

Definitions

  • Printing members for intaglio printing have traditionally had a print surface formed of copper.
  • Recently various proposals have been made to form the print surface of other materials.
  • British Patent Specifications Nos. 1,465,364, 1,498,819 and 1,517,714 it is proposed to form the print surface of two materials, one material defining cells of the required cell pattern and the other material filling the cells and being, for instance, an epoxy resin.
  • the epoxy resin is more easily decomposed or evaporated by a laser beam, used to create the intaglio printing member, than the material defining the cells.
  • Epoxy coatings are also proposed in British Patent Specification No. 1,544,748.
  • epoxy resins are known. For instance it is common to provide powdered epoxy coating compositions based on diglycidyl ethers of bisphenol A. Cycloaliphatic epoxy coating compositions are also known. Another type of epoxy coating composition is an epoxy novolac composition. However such compositions have a tendency to form surfaces having inferior surface properties compared to many other types of epoxy resin. For instance epoxy novolac resins tend to suffer from the increased likelihood of the effect known as "orange peel effect".
  • epoxy novolacs as a component for improving the adhesion between a substrate and a layer to be bonded to it (for instance as in U.S. Patent No. 4210569). Also it is known to blend a urethane formed between a novolac and a polyisocyanate with an epoxy resin, as in British Patent Specification No. 2031442. However this does not form an epoxy novolac.
  • Epoxy novolac resins suitable for use in the invention are applied to a substrate in an uncured or partially cured form and then cured on the substrate to form the desired cured continuous print surface.
  • Epoxy novolacs that are to be cured comprise either a blend of an epoxy with a novolac, that will react on curing, or comprise a novolac resin containing epoxy groups, that will cross-link on curing.
  • One form of epoxy novolac for use in the invention is obtained by reacting a novolac resin with epichlorhydrin, generally in proportions such that the resultant novolac resin is substituted by at least 2 epoxy groups per molecule.
  • a novolac resin with epichlorhydrin, generally in proportions such that the resultant novolac resin is substituted by at least 2 epoxy groups per molecule.
  • it can be regarded as a glycidyl ether of a novolac resin. This is cured on the substrate in the presence of curing agent or accelerator.
  • the other, and preferred, type of novolac resin for use in the invention is a blend of an epoxy resin with at least 0.5 moles novolac resin per mole epoxy resin. This blend is applied to the substrate and is cured on the substrate to complete reaction between the epoxy resin and the novolac resin.
  • the epoxy resin that is reacted with the novolac is preferably based on bisphenol A, generally being a reaction product of epichlorhydrin with bisphenol A. This reaction product may be further reacted with other components, for instance a dimeric carboxylic acid.
  • the novolac resin is preferably used in an amount of at least 1, and preferably 1.1 moles or more novolac per mole epoxy. Best results are generally obtained with around 1.25 moles novolac per mole epoxy although in some instances amounts of up to 2, 3 or even more moles novolac per mole epoxy may be preferred, as explained below.
  • epoxy novolac blended resins will generally include an additional curing agent or accelerator so as to promote the final curing.
  • the phenolic groups from which the novolac is formed may be derived from phenol itself or from substituted phenols, for instance a cresol. It is particularly preferred that the phenol should be substituted by groups additional to the hydroxy group required for forming the novolac and preferably some or all of the benzene groups in the novolac are substituted by additional hydroxy or alkoxy, generally methoxy, groups.
  • the print member is made by applying the curable epoxy novolac composition onto a substrate and then curing it to form the desired continuous print surface and then polishing the print surface to give non-print characteristics.
  • the application is by powder coating of a powdered epoxy novolac composition.
  • the powdered composition, and the print surface that is finally produced from it preferably consists mainly of epoxy novolac, generally in an amount of at least 80% and preferably at least 90% by weight of the composition.
  • the composition will include any necessary curing agents or accelerators for instance an acid anhydride or amine curing agent.
  • the composition may include small amounts, generally below 10%, of conventional flowing agents such as waxes, soaps and alkali metal salts.
  • the composition may contain some filler but the amount should be below 20%, and preferably below 15%, by weight.
  • the composition is preferably totally free of the conventional bulk fillers such as bauxite, alumina or barium sulphate. Whilst it may contain small amounts of various fillers it is particularly preferred that the composition contains carbon black, generally in an amount of from 0.5 to 10%, most preferably 1 to 5%, by weight based on the total composition. As explained in our specification number 2071574 the presence of carbon black reduces the threshold required for laser engraving and so improves the quality of engraving and the maintenance of non-print characteristics between the engraved cells.
  • the composition may also include from 0.05 to 10% by weight, most preferably 0.5 to 5%, of an additive selected from graphite, polytetrafluoroethylene and, most preferably, molybdenum disulphide.
  • an additive selected from graphite, polytetrafluoroethylene and, most preferably, molybdenum disulphide.
  • the powdered composition may be deposited on the substrate by electrostatic coating, floc spraying, fluidised bed coating or, preferably, a combined electrostatic and fluidised bed coating method.
  • electrostatic coating floc spraying, fluidised bed coating or, preferably, a combined electrostatic and fluidised bed coating method.
  • This latter method is particularly advantageous since the electrostatic forces ensure very uniform deposition of a mono particulate layer and the fluidised bed technique results in this uniform sub-layer being built up to a layer of the desired thickness and having great uniformity.
  • the substrate is generally preheated to a temperature at which the powder will fuse upon contact with the substrate, or upon contact with epoxy resin already deposited on the substrate.
  • the composition must be cured by heating on the substrate.
  • the temperature and duration of the heating will be chosen having regard to the particular epoxy novolac and curing agents used, and their relative amounts.
  • the commercially available systems generally require curing at a temperature of 180 to 250°C, preferably 210 to 240°C for periods of half to six hours, preferably two to four hours. However these temperatures and/or times may be reduced by increasing the amount of accelerator in the composition.
  • the substrate is heated to a temperature at which the powdered composition fuses sufficiently to form an adherent layer but at which the composition does not cure.
  • the entire assembly is then heated to a higher temperature at which curing will occur.
  • the substrate is preheated to the curing temperature of the epoxy resin and the epoxy resin is powder coated onto the heated substrate and flows to form a uniform layer of resin that cures substantially without further heating.
  • no external heating is applied and the fusing and curing results entirely from the preheating of the substrate. This is very advantageous as it eliminates the need for heating the print member after the powder coating step.
  • the powdered epoxy novolac composition will have to be formulated, in known manner, to ensure that it does not sag or flow unacceptably at the fusing and curing temperature.
  • the surface obtained by fusing and curing the powdered composition is then polished to give it non-print characteristics in intaglio printing.
  • the substrate and the print surface are cylindrical and the polishing is by diamond turning, but various methods of imparting non-print characteristics to intaglio surfaces are available and can be used.
  • the print surface can then be engraved, generally by ion or electron beam or, preferably, by laser.
  • the print surface must be of a thickness such that it can be engraved to the desired depth.
  • intaglio print surfaces are engraved to a depth of up to 30 microns and the layer of epoxy novolac is generally 0.2 to 1.5 mm, preferably 0.4 to 1 mm and most preferably 0.6 to 0.8 mm thick.
  • the curing conditions (before polishing) will have been selected to give optimum curing of the polymeric composition, which contains epoxy groups. It is well known that further curing of an epoxy composition, by application of high temperature, is generally undesirable as it may give stress cracking or degradation.
  • This further high temperature treatment or curing may be applied to the polished surface before engraving or may be applied to the engraved surface. If it is applied to the polished surface before engraving it is usual to polish the surface again after the post-cure and before engraving.
  • the post-cure is achieved by subjecting the polished surface to high temperature curing, generally at a temperature above the curing temperature that was used before polishing.
  • the temperature is generally from 180 to 280°C, preferably 200 to 260°C and most preferably about 240°C, and is generally applied for periods of half to six hours, preferably 1 to 3 hours. It appears that the heating results in a condensation reaction between phenolic groups of the novolac and consequential expulsion of water. It appears that the reaction only occurs in the outer surface of the layer. It is easy to select the optimum conditions for the heating, after the polishing operation, by routine experimentation and observation of which temperatures and durations give the greatest hardness and scratch resistance.
  • the novolac epoxy resin includes reactive groups capable of entering into condensation reactions. It is therefore desirable for the novolac epoxy resin to contain an excess of novolac, preferably at least 1.25 moles novolac per mole epoxy and preferably considerably more, e.g. up to 2 or 3 or even more moles novolac per mole epoxy. Another way of ensuring particularly good final properties is for the novolac to be formed from a phenol containing more substituents than the single hydroxy group of phenol, for instance it is preferred for the phenolic component to contain at least a second hydroxy group and/or an alkoxy group, preferably a methoxy group.
  • the phenolic component of the novolac is a methoxy or other alkoxy substituted benzene diol or higher polyol and when the phenolic component is present in an amount of at least 1.2 moles per mole epoxy.
  • the epoxy novolac is a highly reactive epoxy novolac containing a significant excess of novolac or containing benzene rings containing additional reactive groups such as hydroxy or methoxy it may be desirable to use a less reactive epoxy novolac to ensure good adhesion between this highly reactive epoxy novolac and the metal or other substrate on which the print surface is formed.
  • a primer layer of, typically, 50 to 175, and generally around 125, microns may be formed of a conventional relatively low functional novolac epoxy and a top coat 150 to 500 microns, typically 200 to 300 microns, may then be applied of the higher functional epoxy, in which the novolac is present in a larger amount and/or is formed from a phenol containing additional hydroxy or other suitable substituents.
  • the primer layer may consist solely of epoxy novolac and curing agent but the outer layer preferably includes carbon black, as mentioned above.
  • the increased wear resistance obtainable as a result of the "case hardening" may be so high as to render it unnecessary to include molybdenum sulphide in the composition of the outer layer.
  • a metal cylinder is heated to 200°C and, while earthed, a powdered epoxy composition is sprayed onto the cylinder using an electrostatic powder spray gun.
  • the composition consists mainly of a phenolic novolac epoxy formed by reaction of a phenolic novolac with epichlorhydrin but contains also conventional curing agent and other additives, but no bulk fillers, 2% benzoin as air release agent, 2% molybdenum sulphide and 5% carbon black, all by weight based on the total composition.
  • the desired coating thickness of about 0.8 mm has been achieved the cylinder and coating are heated at about 220°C for 3 hours in order to fuse and cure the coating. It is then diamond turned and laser engraved and optionally etched and optionally further etched and metal plated as described in British Patent Specification No. 2071574.
  • a cylinder is powder coated as described in Example 1 but using two different compositions.
  • the first composition which is applied to a thickness of 125 microns, is a phenolic novolac epoxy formed by reaction of 1.25 moles of phenolic novolac with epichlorhydrin, the phenol component of the novolac being hydroxy benzene.
  • This primer composition also contains curing agent and air release agent.
  • On top of the primer composition there is applied a layer 250 microns thick of a phenolic novolac epoxy formed by reaction of 1.25 moles phenolic novolac with epichlorhydrin, the phenolic component being methoxy benzene diol.
  • This outer composition also contains curing agent and 5% carbon black. Both compositions are sprayed under conditions of low relative humidity, about 15%.
  • the cylinder and coating are heated at about 220°C for 3 hours in order to fuse and cure the coating.
  • the coating is then diamond turned to give it non-print characteristics and is then further heated for 2 hours at 240°C. It is then laser engraved, and optionally etched. It can then be used for gravure printing.
  • a bisphenol A epichlorhydrin resin is reacted with a dimer acid and 90 parts by weight of the reaction product are blended with 10 parts by weight of a low molecular weight novolac resin formed by reacting formaldehyde with dihydroxy monomethoxy benzene.
  • the blend is heated to cause partial reaction and is then cooled and solidified to terminate reaction and is then cooled and solidified to terminate reaction and to produce a powder.
  • 100 parts of this powder are blended with 6 parts of carbon black, about 0.5 parts benzoin and a small amount of polyacrylic acid flowing agent sold under the trade name Mod- aflow.
  • a metal cylinder is heated to 220°C and the powdered epoxy composition is sprayed onto it using an electrostatic powder spray gun.
  • the metal cylinder may first be coated with a primer, as in example 2.
  • the powdered composition is applied to give a coating thickness of about 0.8 mm and cures on the substrate, while the substrate is cooling towards ambient temperature.
  • the coated substrate is then diamond turned and laser engraved to form an intaglio print surface. It is then heated to 240°C for 3 hours.
  • the resultant print member can be used for a print run in excess of 1 million copies.
  • Example 3 The process of Example 3 is repeated but using an epoxy:novolacweight ratio of7:3 and including additionally a trace amount of 2-methyl imidazole as accelerator.

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Plasma & Fusion (AREA)
  • Manufacturing & Machinery (AREA)
  • Manufacture Or Reproduction Of Printing Formes (AREA)
  • Printing Plates And Materials Therefor (AREA)
  • Epoxy Resins (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (13)

1. Tiefdruckform mit einer Druckoberflächeaus einer Zusammensetzung, die ein Epoxyharz umfaßt und weniger als 20% Füllstoff enthält, dadurch gekennzeichnet, daß das Epoxyharz ein Epoxy-Novolakharz ist, das erhalten wurde entweder durch Härten eines Novolakharzes, welches durch mindestens 2 Epoxygruppen pro Molekül substituiert ist, oder durch Umsetzen eines Epoxyharzes mit mindestens 0,5 Mol Novolakharz pro Mol Epoxyharz.
2. Druckform nach Anspruch 1, bei der der Epoxy-Novolak ein Harz ist, welches erhalten wurde durch Umsetzen von 1 Mol eines Epichlorhydrin-Bisphenol A-Epoxyharzes mit mindestens 1,1 Mol eines Novolakharzes.
3. Verfahren zur Herstellung einer Tiefdruckform durch Auftragen einer härtbaren Epoxyharzzusammensetzung, die weniger als 20% Füllstoff enthält, auf ein Substrat und anschließendes Härten des Überzugs und Polieren der Druckoberfläche, um ihr Nicht-Druckeigenschaften zu verleihen, dadurch gekennzeichnet, daß das härtbare Epoxyharz eine Epoxy-Novolakzusammensetzung ist, welche eine Mischung eines Härters mit einem Novolakharz, das durch mindestens 2 Epoxygruppen substituiert ist, darstellt, oder erhalten wird durch Mischen eines Epoxyharzes mit mindestens 0,5 Mol Novolakharz pro Mol Epoxyharz.
4. Verfahren nach Anspruch 3, dadurch gekennzeichnet, daß die Zusammensetzung durch Pulverbeschichtung einer pulverförmigen Epoxy-Novolakharzzusammensetzung aufgetragen wird.
5. Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß das Substrat auf die Härtungstemperatur des Epoxy-Novolakharzes vorerhitzt wird und das pulverförmige Harz durch Pulverbeschichtung auf das erhitzte Substrat aufgebracht wird, zu einer gleichmäßigen Schicht der gewünschten Dicke zerfließt und ohne wesentliches weiteres Erhitzen härtet.
6. Verfahren nach irgendeinem der Ansprüche 3 bis 5, dadurch gekennzeichnet, daß die Epoxy-Novolakzusammensetzung eine Zusammensetzung ist, die erhalten wurde durch Mischen von 1 Mol eines Epichlorhydrin-Bisphenol A-Epoxyharzes mit mindestens 1,1 Mol eines Novolakharzes.
7. Verfahren nach irgendeinem der Ansprüche 3 bis 6, dadurch gekennzeichnet, daß die Druckoberfläche nach dem Polieren erhitzt wird, um eine weitere Härtung der Oberfläche der Epoxyharzschicht zu bewirken.
8. Verfahren nach Anspruch 7, dadurch gekennzeichnet, daß das Erhitzen nach dem Polieren 1/2 bis 6 Stunden bei einer Temperatur von 200 bis 260°C durchgeführt wird.
9. Verfahren nach Anspruch 7 oder Anspruch 8, bei dem das Novolakharz aus einem Phenol hergestellt wird, das durch mindestens eines zusätzliche Hydroxygruppe und/oder eine Alkoxygruppe substituiert ist.
10. Verfahren nach Anspruch 7 oder Anspruch 8, bei dem der Novolak aus einem Methoxy substituierten ein-oder zweiwertigen Phenol hergestellt wird.
11. Verfahren nach irgendeinem der Ansprüche 7 bis 10, bei dem das Epoxyharz aus 1 Mol Bisphenol A-Epichlorohydrinharz und 1,25 bis 3 Mol eines Novolakharzes hergestellt wird.
12. Verfahren nach irgendeinem der Ansprüche 7 bis 11, bei dem das weitere Erhitzen nach dem Gravieren der Oberfläche durchgeführt wird.
13. Verfahren nach irgendeinem der Ansprüche 3 bis 12, dadurch gekennzeichnet, daß die Druckoberfläche nach dem Polieren mit Laserstrahlen graviert wird.
EP83301216A 1982-03-15 1983-03-07 Druckplatte und Verfahren zu ihrer Herstellung Expired EP0094142B1 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB8207530 1982-03-15
GB8207530 1982-03-15
GB8216565 1982-06-08
GB8216565 1982-06-08

Publications (2)

Publication Number Publication Date
EP0094142A1 EP0094142A1 (de) 1983-11-16
EP0094142B1 true EP0094142B1 (de) 1986-09-03

Family

ID=26282252

Family Applications (1)

Application Number Title Priority Date Filing Date
EP83301216A Expired EP0094142B1 (de) 1982-03-15 1983-03-07 Druckplatte und Verfahren zu ihrer Herstellung

Country Status (5)

Country Link
US (1) US4528909A (de)
EP (1) EP0094142B1 (de)
CA (1) CA1217687A (de)
DE (1) DE3365783D1 (de)
ES (1) ES8403787A1 (de)

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GB8421525D0 (en) * 1984-08-24 1984-09-26 Ciba Geigy Ag Powder coating compositions
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US4745020A (en) * 1986-07-08 1988-05-17 Electro-Voice, Incorporated Engraved plastic article
US4824715A (en) * 1986-07-08 1989-04-25 Electro-Voice, Incorporated Engraving process and product thereof
DE3637642A1 (de) * 1986-11-05 1988-05-11 Kissel & Wolf Gmbh Verfahren zur herstellung von druckformen fuer den siebdruck
GB2198085B (en) * 1986-11-29 1991-02-13 Stc Plc Printing apparatus and process
NL8701176A (nl) * 1987-05-15 1988-12-01 Stork Screens Bv Dessineerdeklaag voor een metalen zeefdruksjabloon; zeefdruksjabloon voorzien van een dessineerdeklaag en werkwijze voor het aanbrengen van een dessineerpatroon in een deklaag welke aanwezig is op een metalen zeefdruksjabloon.
DE3730193A1 (de) * 1987-09-09 1989-03-23 Bonner Zeitungsdruckerei Druckform, insbesondere druckplatte und hochdruckverfahren
US5694852A (en) * 1990-04-26 1997-12-09 W.R. Chesnut Engineering, Inc. Rotogravure printing media and methods of manufacturing a rotogravure printing device employing the media
DE69125276T2 (de) * 1990-04-26 1997-09-25 Chesnut Eng Tiefdruckplattenmaterial und verfahren zur herstellung einer tiefdruckvorrichtung unter verwendung dieses materials
DE4023566C1 (de) * 1990-07-25 1991-09-19 Rudolf 7129 Brackenheim De Fleischle
US5804353A (en) * 1992-05-11 1998-09-08 E. I. Dupont De Nemours And Company Lasers engravable multilayer flexographic printing element
US5798202A (en) * 1992-05-11 1998-08-25 E. I. Dupont De Nemours And Company Laser engravable single-layer flexographic printing element
FR2693205B1 (fr) * 1992-07-02 1994-09-02 Inst Francais Du Petrole Compositions de revêtement gravables notamment pour rouleaux d'imprimerie, procédé d'enduction et objets fabriqués par ce procédé.
JP3500182B2 (ja) * 1994-04-04 2004-02-23 ソニー株式会社 レーザー製版用版材料
US6631676B2 (en) * 1995-02-07 2003-10-14 Man Roland Druckmaschinen Ag Process and apparatus for gravure
US5934197A (en) * 1997-06-03 1999-08-10 Gerber Systems Corporation Lithographic printing plate and method for manufacturing the same
ATE270191T1 (de) * 2000-12-19 2004-07-15 Basf Drucksysteme Gmbh Verfahren zur herstellung von flexodruckformen mittels lasergravur
US7126619B2 (en) * 2002-05-31 2006-10-24 Buzz Sales Company, Inc. System and method for direct laser engraving of images onto a printing substrate
KR101010431B1 (ko) * 2003-12-27 2011-01-21 엘지디스플레이 주식회사 평판표시소자의 제조방법 및 장치
EP2522509A3 (de) * 2011-05-12 2013-12-04 E. I. du Pont de Nemours and Company Druckform und Verfahren zur Herstellung der Druckform mittels einer härtbaren Zusammensetzung mit Expoxy-Novolac-Harz
US20120285342A1 (en) * 2011-05-12 2012-11-15 E.I. Du Pont De Nemours And Company Printing form and process for preparing the printing form with curable composition having bisphenol-based epoxy resin
US9096759B2 (en) 2011-12-21 2015-08-04 E I Du Pont De Nemours And Company Printing form and process for preparing the printing form with curable composition having solvent-free epoxy resin
WO2014074431A1 (en) * 2012-11-09 2014-05-15 E. I. Du Pont De Nemours And Company A printing form and a process for preparing a printing form
US20140251168A1 (en) * 2013-03-06 2014-09-11 E I Du Pont De Nemours And Company Printing form and a process for preparing a printing form using two-step cure

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GB2071574B (en) * 1980-03-11 1984-09-05 Crosfield Electronics Ltd Printing members

Also Published As

Publication number Publication date
ES520625A0 (es) 1984-04-01
DE3365783D1 (en) 1986-10-09
EP0094142A1 (de) 1983-11-16
US4528909A (en) 1985-07-16
ES8403787A1 (es) 1984-04-01
CA1217687A (en) 1987-02-10

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